Polyolefin catalysts

ABSTRACT

This invention is directed to novel Group 8-10 transition metal catalysts and to batch or continuous polymerizations using these catalysts. The catalysts of the present invention readily convert ethylene and α-olefins to high molecular weight polymers, and allow for olefin polymerizations under various conditions, including ambient temperature and pressure, and in solution. Preferred catalysts are group 8-10 transition metals having certain dipyridyl ligands bonded thereto.

This is a divisional application of application Ser. No. 09/145,530,filed Sep. 2, 1998, now U.S. Pat. No. 6,117,959.

FIELD OF THE INVENTION

The present invention is directed to Group 8-10 transitionmetal-containing complexes and their use in olefin polymerizations.

BACKGROUND OF THE INVENTION

Olefin polymers are used in a wide variety of products, from sheathingfor wire and cable to film. Olefin polymers are used, for instance, ininjection or compression molding applications, in extruded films orsheeting, as extrusion coatings on paper, for example photographic paperand digital recording paper, and the like. Improvements in catalystshave made it possible to better control polymerization processes, and,thus, influence the properties of the bulk material. Increasingly,efforts are being made to tune the physical properties of plastics forlightness, strength, resistance to corrosion, permeability, opticalproperties, and the like, for particular uses. Chain length, polymerbranching and functionality have a significant impact on the physicalproperties of the polymer. Accordingly, novel catalysts are constantlybeing sought in attempts to obtain a catalytic process for polymerizingolefins which permits more efficient and better controlledpolymerization of olefins.

Conventional polyolefins are prepared by a variety of polymerizationtechniques, including homogeneous liquid phase, gas phase, and slurrypolymerization. Certain transition metal catalysts, such as those basedon titanium compounds (e.g. TiCl₃ or TiCl₄) in combination withorganoaluminum cocatalysts, are used to make linear and linear lowdensity polyethylenes as well as poly-α-olefins such as polypropylene.These so-called “Ziegler-Natta” catalysts are quite sensitive to oxygenand are ineffective for the copolymerization of nonpolar and polarmonomers.

Recent advances in non-Ziegler-Natta olefin polymerization catalysisinclude the following.

L. K. Johnson et al., WO Patent Application 96/23010, disclose the,polymerization of olefins using cationic nickel, palladium, iron, andcobalt complexes containing diimine and bisoxazoline ligands. Thisdocument also describes the polymerization of ethylene, acyclic olefins,and/or selected cyclic olefins and optionally selected unsaturated acidsor esters such as acrylic acid or alkyl acrylates to provide olefinhomopolymers or copolymers.

European Patent Application Serial No. 381,495 describes thepolymerization of olefins using palladium and nickel catalysts whichcontain selected bidentate phosphorous containing ligands.

L. K. Johnson et al., J. Am. Chem. Soc., 1995, 117, 6414, describe thepolymerization of olefins such as ethylene, propylene, and 1-hexeneusing cationic α-diimine-based nickel and palladium complexes. Thesecatalysts have been described to polymerize ethylene to high molecularweight branched polyethylene. In addition to ethylene, Pd complexes actas catalysts for the polymerization and copolymerization of olefins andmethyl acrylate.

G. F. Schmidt et al., J. Am. Chem. Soc. 1985, 107, 1443, describe acobalt(III) cyclopentadienyl catalytic system having the structure[C₅Me₅(L)CoCH₂CH₂-μ-H]⁺, which provides for the “living” polymerizationof ethylene.

M. Brookhart et al., Macromolecules 1995, 28, 5378, disclose using such“living” catalysts in the synthesis of end-functionalized polyethylenehomopolymers.

U. Klabunde, U.S. Pat. Nos. 4,906,754, 4,716,205, 5,030,606, and5,175,326, describes the conversion of ethylene to polyethylene usinganionic phosphorous, oxygen donors ligated to Ni(II). The polymerizationreactions were run between 25 and 100° C. with modest yields, producinglinear polyethylene having a weight-average molecular weight rangingbetween 8K and 350K. In addition, Klabunde describes the preparation ofcopolymers of ethylene and functional group containing monomers.

M. Peuckert et al., Organomet. 1983, 2(5), 594, disclose theoligomerization of ethylene using phosphine, carboxylate donors ligatedto Ni(II), which showed modest catalytic activity (0.14 to 1.83 TO/s).The oligomerizations were carried out at 60 to 95° C. and 10 to 80 barethylene in toluene, to produce linear α-olefins.

R. E. Murray, U.S. Pat. Nos. 4,689,437 and 4,716,138, describes theoligomerization of ethylene using phosphine, sulfonate donors ligated toNi(II). These complexes show catalyst activities approximately 15 timesgreater than those reported with phosphine, carboxylate analogs.

W. Keim et al., Angew. Chem. Int. Ed. Eng. 1981, 20, 116, and V. M.Mohring, et al., Angew. Chem. Int. Ed. Eng. 1985, 24, 1001, disclose thepolymerization of ethylene and the oligomerization of α-olefins withaminobis(imino)phosphorane nickel catalysts; G. Wilke, Angew. Chem. Int.Ed. Engl. 1988, 27, 185, describes a nickel allyl phosphine complex forthe polymerization of ethylene.

K. A. O. Starzewski et al., Angew. Chem. Int. Ed. Engl. 1987, 26, 63,and U.S. Pat. No. 4,691,036, describe a series of bis(ylide) nickelcomplexes, used to polymerize ethylene to provide high molecular weightlinear polyethylene.

WO Patent Application 97/02298 discloses the polymerization of olefinsusing a variety of neutral N, O, P, or S donor ligands, in combinationwith a nickel(0) compound and an acid.

Brown et al., WO 97/17380, describes the use of Pd α-diimine catalystsfor the polymerization of olefins including ethylene in the presence ofair and moisture.

Fink et al., U.S. Pat. No., 4,724,273, have described the polymerizationof α-olefins using aminobis(imino)phosphorane nickel catalysts and thecompositions of the resulting poly(α-olefins).

Recently Vaughan et al., WO 97/48736, Denton et al., WO 97/48742, andSugimura et al., WO 97/38024 have described the polymerization ofethylene using silica supported α-diimine nickel catalysts.

Additional recent developments are described by Sugimura et al., inJP96-84344, JP96-84343, by Yorisue et al., in JP96-70332, by Canich etal., WO 97148735, McLain et al., WO 98/03559, Weinberg et al., WO98/03521 and by Matsunaga et al., WO 97/48737.

Notwithstanding these advances in non-Ziegler-Natta catalysis, thereremains a need for efficient and effective Group 8-10 transition metalcatalysts for effecting polymerization of olefins. In addition, there isa need for novel methods of polymerizing olefins employing sucheffective Group 8-10 transition metal catalysts. In particular, thereremains a need for Group 8-10 transition metal olefin polymerizationcatalysts with both improved temperature stability and functional groupcompatibility. Further, there remains a need for a method ofpolymerizing olefins utilizing effective Group 8-10 transition metalcatalysts in combination with a Lewis acid so as to obtain a catalystthat is more active and more selective.

SUMMARY OF THE INVENTION

The present invention is directed to novel Group 8-10 transition metalcatalysts and to batch or continuous polymerizations using thesecatalysts. The catalysts used in the processes of the present inventionreadily convert ethylene and α-olefins to high molecular weightpolymers, and allow for olefin polymerizations under various conditions,including ambient temperature and pressure, and in solution. Preferredcatalysts include certain dipyridyl ligands coordinated to Group 8-10transition metals.

The catalysts and processes of the present invention are useful in thepreparation of homopolymers of olefins, such as polyethylene,polypropylene, and the like, and olefin copolymers. As an example,ethylene homopolymers can be prepared with strictly linear to highlybranched structures by variation of the catalyst structure, cocatalystcomposition, and reaction conditions, including pressure andtemperature. The effect these parameters have on polymer structure isdescribed herein. These polymers and copolymers have a wide variety ofapplications, including use as packaging materials and in adhesives.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a process for the polymerization ofolefins, comprising contacting one or more monomers selected fromcompounds of the formula R²CH═CHR² with a catalyst comprising (a) aNi(II), Pd(II), Co(II), or Fe(II) metal atom, (b) a ligand of theformula I, and optionally (c) a Bronsted or Lewis acid,

wherein

R¹ and R² are each, independently, hydrogen, hydrocarbyl, orfluoroalkyl, and may be linked to form a cyclic olefin;

L¹ and L² are each, independently, a 5- or 6-membered, monodentateN-donor, heterocyclic ring connected to Q at the position adjacent tothe donor nitrogen; and

Q is a group of the formula —C(Y)(Z)— wherein Z is H or a heteroatomconnected monoradical and Y is hydrocarbyl or substituted hydrocarbyl.

In the above process, it should be appreciated that the Group 8-10transition metal has coordinated thereto a bidentate ligand having theformula I and that component (c) is optionally reacted with thismetal-ligand complex.

As a further aspect of the invention, there is provided a process forthe polymerization of olefins, comprising contacting one or moremonomers of the formula R¹CH═CHR² with a catalyst of formula II:

wherein

R¹ and R² are each, independently, hydrogen, hydrocarbyl, orfluoroalkyl, and may be linked to form a cyclic olefin;

L¹ and L² are each, independently, a 5- or 6-membered, monodentateN-donor, heterocyclic ring connected to Q at the position adjacent tothe donor nitrogen;

Q is a group of the formula —C(Y)(Z)— wherein Z is H or a heteroatomconnected monoradical and Y is hydrocarbyl or substituted hydrocarbyl;

T is hydrogen or hydrocarbyl;

L is a mono-olefin or a neutral Lewis base wherein the coordinated atomis nitrogen, oxygen, or sulfur;

M is Ni(II), Pd(II), Co(II), or Fe(II); and

X⁻ is a weakly coordinating anion.

We believe that when T is hydrogen or hydrocarbyl and L is ethylene or amono-olefin in formula II above, then II is the catalytically activespecies. This active species can be prepared by a number of differentmethodologies, including reaction of a zero-valent metal complex with aligand of formula I and a Bronsted acid in the presence of ethylene or amono-olefin. An example of this methodology includes the reaction ofbis(cyclooctadiene)Ni(0) with a bidentate ligand of formula I andhydrogen tetrakis[3,5-(bistrifluoromethyl)phenyl]borate in the presenceof ethylene or a mono-olefin to generate an active catalyst of formulaII.

In a further aspect of the invention, there is provided a process forthe polymerization of olefins, comprising contacting one or moremonomers of the formula R¹CH═CHR² with a catalyst formed by combining acompound of formula III:

with a compound A, wherein

R¹ and R² are each, independently, H, hydrocarbyl, or fluoroalkyl, andmay be linked to form a cyclic olefin;

L¹ and L² are each, independently, a 5- or 6-membered, monodentateN-donor, heterocyclic ring connected to Q at the position adjacent tothe donor nitrogen;

Q is a group of the formula —C(Y)(Z)— wherein Z is H or a heteroatomconnected monoradical and Y is hydrocarbyl or substituted hydrocarbyl;

U is alkyl, chloride, iodide or bromide;

W is alkyl, chloride, iodide or bromide;

M is Ni(II), Pd(II), Co(II), or Fe(II); and,

A is selected from the group consisting of a neutral Lewis acid capableof abstracting U⁻ or W⁻ to form a weakly coordinating anion, a cationicLewis acid whose counterion is a weakly coordinating anion, and aBronsted acid whose conjugate base is a weakly coordinating anion.

As a further example of a methodology useful to prepare thecatalytically active specie II includes, when U and W are bothindependently bromide, the complex III can be reacted with a compound A(e.g., an alkyl aluminum specie, such as methylaluminoxane (MAO)), inthe presence of ethylene or a mono-olefin to provide the active catalystof formula II.

Also provided are the catalysts described above. Accordingly, as afurther aspect of the invention there is provided a compound of formulaII:

wherein

L¹ and L² are each, independently, a 5- or 6-membered, monodentateN-donor, heterocyclic ring connected to Q at the position adjacent tothe donor nitrogen;

Q is a group of the formula —C(Y)(Z)— wherein Z is H or a heteroatomconnected monoradical and Y is hydrocarbyl or substituted hydrocarbyl;

T is H or hydrocarbyl;

L is a mono-olefin or a neutral Lewis base wherein the coordinated atomis nitrogen, oxygen, or sulfur;

M is Ni(II), Pd(II), Co(II), or Fe(II); and

X⁻ is a weakly coordinating anion.

Also provided is a compound of formula III:

wherein

L¹ and L² are each, independently, a 5- or 6-membered, monodentateN-donor, heterocyclic ring connected to Q at the position adjacent tothe donor nitrogen;

Q is a group of the formula —C(Y)(Z)— wherein Z is H or a heteroatomconnected monoradical and Y is hydrocarbyl or substituted hydrocarbyl;

U is alkyl, chloride, iodide, or bromide;

W is alkyl, chloride, iodide, or bromide; and

M is Ni(II), Pd(II), Co(II), or Fe(II).

Also provided is a composition comprising (a) a Group 8-10 transitionmetal M, (b) one or more Lewis acids, and (c) a binucleating ormultinucleating compound of the formula I:

wherein

the Lewis acid or acids are bound to one or more heteroatoms which areπ-conjugated to the donor atom or atoms bound to the transition metal M;

L¹ and L² are each, independently, a 5- or 6-membered, monodentateN-donor, heterocyclic ring connected to Q at the position adjacent tothe donor nitrogen;

Q is a group of the formula —C(Y)(Z)— wherein Z is H or a heteroatomconnected monoradical and Y is hydrocarbyl or substituted hydrocarbyl.

In this disclosure certain chemical groups or compounds are described bycertain terms and symbols. These terms are defined as follows:

Symbols ordinarily used to denote elements in the Periodic Table taketheir ordinary meaning, unless otherwise specified. Thus, N, O, S, P,and Si stand for nitrogen, oxygen, sulfur, phosphorus, and silicon,respectively.

Examples of neutral Lewis acids include, but are not limited to,methylaluminoxane (hereinafter MAO) and other aluminum sesquioxides, R⁷₃Al, R⁷ ₂AlCl, R⁷AlCl₂ (where R⁷ is alkyl), organoboron compounds, boronhalides, B(C₆F₅)₃, BPh₃, and B(3,5-(CF₃)C₆H₃)₃. Examples of ioniccompounds comprising a cationic Lewis acid include: R⁹ ₃Sn[BF₄], (whereR⁹ is hydrocarbyl), MgCl₂, and H⁺X⁻, where X⁻ is a weakly coordinatinganion.

Examples of neutral Lewis bases include, but are not limited to, (i)ethers, for example, diethyl ether or tetrahydrofuran, (ii) organicnitrites, for example acetonitrile, (iii) organic sulfides, for exampledimethylsulfide, or (iv) monoolefins, for example, ethylene, hexene orcyclopentene.

A “hydrocarbyl” group means a monovalent or divalent, linear, branchedor cyclic group which contains only carbon and hydrogen atoms. Examplesof monovalent hydrocarbyls include the following: C₁-C₂₀ alkyl; C₁-C₂₀alkyl substituted with one or more groups selected from C₁-C₂₀ alkyl,C₃-C₈ cycloalkyl or aryl; C₃-C₈ cycloalkyl; C₃-C₈ cycloalkyl substitutedwith one or more groups selected from C₁-C₂₀ alkyl, C₃-C₈ cycloalkyl oraryl; C₆-C₁₄ aryl; and C₆-C₁₄ aryl substituted with one or more groupsselected from C₁-C₂₀ alkyl, C₃-C₈ cycloalkyl or aryl; where the term“aryl” preferably denotes a phenyl, napthyl, or anthracenyl group.Examples of divalent (bridging) hydrocarbyls include: —CH₂—, —CH₂CH₂—,—CH₂CH₂CH₂—, and 1,2-phenylene.

A “heteroatom” refers to an atom other than carbon or hydrogen.Preferred heteroatoms include oxygen, nitrogen, phosphorus, sulfur,selenium, arsenic, chlorine, bromine, silicon and fluorine.

A “substituted hydrocarbyl” refers to a monovalent or divalenthydrocarbyl substituted with one or more heteroatoms. Examples ofmonovalent substituted hydrocarbyls include: —C(O)R¹³ (wherein R¹³ ishydrocarbyl), —C(O)NR¹³ ₂ (wherein R¹³ is hydrocarbyl), 2-hydroxyphenyl,2-methoxyphenyl, 2-ethoxyphenyl, 2-fluorophenyl, 2-chlorophenyl,2-trifluoromethylphenyl, 2,6-bis(trifluoromethyl)phenyl,2-(trialkylsiloxy)phenyl, 2-(triarylsiloxy)phenyl,2,6-bis(diphenylamino)phenyl, 2,6-bis(phenoxy)phenyl,2-hydroxy-6-phenylphenyl, 2-cyanophenyl, 2-(diphenylamino)phenyl,4-nitrophenyl, 2-nitrophenyl, —CH₂OR¹³ (wherein R¹³ is hydrocarbyl),cyano, —CH₂NR¹³ ₂ (wherein R¹³ is hydrocarbyl), and —H₂OSiR¹³ ₃ (whereinR¹³ is hydrocarbyl).

A “monodentate N-donor, heterocyclic ring” refers to an aromaticsubstituted hydrocarbyl ring containing at least one sp² hybridizednitrogen atom, which provides a single point of coordination to thetransition metal M, and which optionally may contain additionalheteroatoms which are π-conjugated to the nitrogen that is bound to thetransition metal M, in the ring. While not wishing to be bound bytheory, the present inventors believe certain Lewis acid cocatalysts(e.g. alkyl aluminum species such as trimethylaluminum or MAO) maycoordinate to said additional heteroatoms, thereby rendering thecatalysts herein more active or more selective or both. A nonlimitingexample of this secondary Lewis acid binding would include thefollowing:

wherein T, L, M, and X are as defined above. Preferred examples ofmonodentate N-donor heterocyclic rings include:

wherein E is selected from H, OCH₃, NO₂, CN, SO₂R⁶, CO₂R⁶, and CONR⁶ ₂where R⁶ is hydrocarbyl or substituted hydrocarbyl; and, R⁵ ishydrocarbyl or substituted hydrocarbyl. More preferred monodentateN-donor heterocycles include:

wherein:

R⁵ is hydrocarbyl or substituted hydrocarbyl.

A “heteroatom connected monoradical” refers to a mono-radical group inwhich a heteroatom serves as the point of attachment. Examples include:—OH, —O(hydrocarbyl), —O(subtituted hydrocarbyl), —O(aluminum), —O(solidsupport), —N(C₆H₅)₂, —NH(C₆H₅), —SH, —Cl, —F and SPh, where Ph isphenyl.

A “mono-olefin” refers to a hydrocarbon containing one carbon-carbondouble bond.

The term “fluoroalkyl” as used herein refers to a C₁-C₂₀ alkyl groupsubstituted by one or more fluorine atoms.

The term “polymer” as used herein is meant a species comprised ofmonomer units and having a degree of polymerization (DP) of ten orhigher.

The term “α-olefin” as used herein is a 1-alkene with from 3 to 40carbon atoms.

The term “weakly coordinating anion” is well-known in the art per se andgenerally refers to a large bulky anion capable of delocalization of thenegative charge of the anion. Suitable weakly coordinating anionsinclude, but are not limited to alkyl aluminates, the anion formed fromthe reaction of MAO and a halogen ligated metal complex, PF₆ ⁻, BF₄ ⁻,SbF₆ ⁻, (Ph)₄B⁻ wherein Ph=phenyl, and ⁻BAr₄ wherein⁻BAr₄=tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. The coordinatingability of such anions is known and described in the literature(Strauss, S. et al., Chem. Rev. 1993, 93, 927).

As used herein, the terms “monomer” or “olefin monomer” refer to theolefin or other monomer compound before it has been polymerized; theterm “monomer units” refers to the moieties of a polymer that correspondto the monomers after they have been polymerized.

In some cases, a compound A is required as a cocatalyst. Suitablecompounds A include a neutral Lewis acid capable of abstracting Q⁻ or W⁻to form a weakly coordinating anion, a cationic Lewis acid whosecounterion is a weakly coordinating anion, or a Bronsted acid whoseconjugate base is a weakly coordinating anion. Preferred compounds Ainclude: methylaluminoxane (hereinafter MAO) and other aluminumsesquioxides, R⁷ ₃Al, R⁷ ₂AlCl, R⁷AlCl₂ (wherein R⁷ is alkyl),organoboron compounds, boron halides, B(C₆F₅)₃, R⁹ ₃Sn[BF₄] (wherein R⁹is hydrocarbyl), MgCl₂, and H⁺X⁻, wherein X⁻ is a weakly coordinatinganion.

Examples of “solid support” include inorganic oxide support materials,such as: talcs, silicas, titania, silica/chromia,silicalchromia/titania, silica/alumina, zirconia, aluminum phosphategels, silanized silica, silica hydrogels, silica xerogels, silicaaerogels, and silica co-gels. An especially preferred solid support isone which has been pre-treated with A compounds as described herein,most preferably with MAO. Thus, in a preferred embodiment, the catalystsof the present invention are attached to a solid support (by “attachedto a solid support” is meant ion paired with a component on the surface,adsorbed to the surface or covalently attached to the surface) which hasbeen pre-treated with an A compound. In an especially preferredembodiment, the compounds of the present invention are attached tosilica which has been pretreated with MAO. Such supported catalysts areprepared by contacting the compound, in an inert solvent—by which ismeant a solvent which is either unreactive under the conditions ofcatalyst preparation, or if reactive, acts to usefully modify thecatalyst activity or selectivity—with MAO treated silica for asufficient period of time to generate the supported catalysts. Examplesof unreactive solvents include toluene, mineral spirits and hexane.Examples of potentially reactive solvents include CH₂Cl₂ and CHCl₃.

Thus, in a further preferred embodiment of the invention, there isprovided a supported catalyst comprising the reaction product of acompound of formula III

wherein

L¹ and L² are each, independently, a 5- or 6-membered, monodentateN-donor, heterocyclic ring connected to Q at the position adjacent tothe donor nitrogen;

Q is a group of the formula —C(Y)(Z)— wherein Z is H or a heteroatomconnected monoradical and Y is hydrocarbyl or substituted hydrocarbyl;

U is alkyl, chloride, iodide or bromide;

W is alkyl, chloride, iodide or bromide;

M is Ni(II), Pd(II), Co(II), or Fe(II); and,

with a solid support which has been pre-treated with a compound A,wherein A is selected from the group consisting of a neutral Lewis acidcapable of abstracting U⁻ or W⁻ to form a weakly coordinating anion, acationic Lewis acid whose counterion is a weakly coordinating anion, anda Bronsted acid whose conjugate base is a weakly coordinating anion.

In general, ligands of formula I can be synthesized by nucleophilicaddition of a Grignard reagent, which can be prepared in situ from thecorresponding aryl or alkyl bromide and Mg turnings, on adi-heterocyclic ketone. The diheterocyclic ketones can be purchased andused without further purification, or prepared according to theprocedure of Newkome, et al. (Newkome, G. R., Joo, Y. J., Evans, D. W.,Pappalardo, S., Fronczek, F. R., J. Org. Chem. 1988, 53, 786-790) from aheterocyclic substituted acetonitrile, as in the following example(scheme I-mCPBA denotes meta-chloro perbenzoic acid and DMF denotesN,N-dimethylformamide):

The polymerizations may be conducted as solution polymerizations, asnon-solvent slurry type polymerizations, as slurry polymerizations usingone or more of the olefins or other solvent as the polymerizationmedium, or in the gas phase. One of ordinary skill in the art, with thepresent disclosure, would understand that the catalyst could besupported using a suitable catalyst support and methods known in theart. Substantially inert solvents, such as toluene, hydrocarbons,methylene chloride and the like, may be used. Propylene and 1-butene areexcellent monomers for use in slurry-type copolymerizations and unusedmonomer can be flashed off and reused.

Temperature and olefin pressure have significant effects on copolymerstructure, composition, and molecular weight. Suitable polymerizationtemperatures are preferably from about −100° C. to about 200° C., morepreferably in the 20° C. to 150° C. range.

After the reaction has proceeded for a time sufficient to produce thedesired polymers, the polymer can be recovered from the reaction mixtureby routine methods of isolation and/or purification.

In general, the polymers of the present invention are useful ascomponents of thermoset materials, as elastomers, as packagingmaterials, films, compatibilizing agents for polyesters and polyolefins,as a component of tackifying compositions, and as a component ofadhesive materials.

High molecular weight resins are readily processed using conventionalextrusion, injection molding, compression molding, and vacuum formingtechniques well known in the art. Useful articles made from them includefilms, fibers, bottles and other containers, sheeting, molded objectsand the like.

Low molecular weight resins are useful, for example, as synthetic waxesand they may be used in various wax coatings or in emulsion form. Theyare also particularly useful in blends with ethylene/vinyl acetate orethylenelmethyl acrylate-type copolymers in paper coating or in adhesiveapplications.

Although not required, typical additives used in olefin or vinylpolymers may be used in the new homopolymers and copolymers of thisinvention. Typical additives include pigments, colorants, titaniumdioxide, carbon black, antioxidants, stabilizers, slip agents, flameretarding agents, and the like. These additives and their use in polymersystems are known per se in the art.

The molecular weight data presented in the following examples isdetermined by gel permeation chromatography (GPC) at 135° C. in1,2,4-trichlorobenzene using refractive index detection, calibratedusing narrow molecular weight distribution poly(styrene) standards.

EXAMPLES Example 1

Synthesis of VI: A solution of 2-bromobiphenyl (740 μl, 4.29 mmol) indiethyl ether (Et₂O) (4 ml) was slowly added to a suspension of Mg (125mg, 5.14 mmol) in Et₂O (4 ml). A crystal of iodine and 1,2-dibromoethane(70 μl) were added, and the suspension was heated to reflux for 1 hour.The resulting suspension was cooled to room temperature and treated witha solution of di-2-pyridyl ketone (788 mg, 4.28 mmol) in Et₂O (8 ml),which resulted in the immediate formation of an orange precipitate. THF(10 ml) was added to dilute the suspension. The reaction was stirred atroom temperature overnight, quenched with saturated aqueous NaHCO₃ (25ml) and concentrated in vacuo. The residue was partitioned between H₂O(25 ml) and CHCl₃ (25 ml). The aqueous layer was further extracted withCHCl₃ (2×25 ml). The combined organic layers were washed with saturatedaqueous Na₂S₂O₃ (25 ml) and brine (25 ml), dried over Na₂SO₄, filteredand concentrated in vacuo to afford the tertiary alcohol VI (1.37 g)contaminated with a small amount of 2-dipyridyl ketone: FDMS m/z 338(M+).

Example 2

Synthesis of VII: VI (107 mg, 0.32 mmol) was charged to a 50 ml flamedried Sclenk tube, and pumped into an Ar filled dry box. In the box,(dimethoxyethane(DME))NiBr₂ (77 mg, 0.25 mmol) was added, the tube wascapped with a septum and removed from the box. CH₂Cl₂ (15 ml) was addedvia syringe. The reaction was stirred at room temperature overnight, andconcentrated under a stream of Ar. The resulting solid was washed withhexanes (2×10 ml), and dried in vacuo to afford VII as a green solid.

Example 3

Ethylene Polymerization with VII: The dibromide complex VII (10 mg,0.018 mmol) was suspended in toluene (50 ml). The suspension wasequilibrated at room temperature under 1 atm of ethylene for 15 min,then treated with methylaluminoxane (MAO) (2 ml, 10 wt % solution intoluene) and stirred vigorously under 1 atm ethylene. The reactionexothermed to 50° C. After 10 min, the reaction was quenched by theaddition of acetone, methanol and 6 N HCl. The toluene layer wasseparated and concentrated in vacuo to afford 760 mg of polyethylene(9100 TO/hr) (TO/hr=turnovers per hour). ¹H NMR (300 MHz, CDCl₃) ˜80-100branches/1000 C's, M_(n)=4500; gas phase chromatography (GPC)M_(n)=3550, M_(w)=7950.

Example 4

Ethylene Polymerization with VII: The dibromide complex VII (9 mg, 0.016mmol) was suspended in toluene (50 ml). The suspension was equilibratedat 0° C. in an ice water bath under 1 atm of ethylene, then treated withMAO (2 ml, 10 wt % solution in toluene) and stirred vigorously under 1atm of ethylene at 0° C. After 2 hr., the reaction was quenched bysequential addition of acetone, methanol and 6 N HCl. The resultingpolymer was filtered and dried in vacuo to to afford 1.42 g ofpolyethylene (1600 TO/hr). ¹H NMR (400 MHz, o-dichlorobenzene-d₄) 41branches/1000 C's, M_(n)=16,400; GPC M_(n)=13,100, M_(w)=50,700.

Example 5

Ethylene Polymerization with VII: The dibromide complex VII (10 mg,0.018 mmol) was suspended in toluene (100 ml) in a Fisher pressurebottle. The suspension was equilibrated at 0° C. under 20 psig ethylenefor 10 min, then treated with MAO (2 ml, 10 wt % solution in toluene)and stirred vigorously under 60 psig ethylene at 0° C. After 80 min.,the reaction was quenched by the sequential addition of acetone,methanol, and 6 N HCl. The resulting polymer was collected by filtrationand dried to afford 542 mg of polyethylene (811 TO/hr). ¹H NMR (400 MHz,o-dichlorobenzene-d₄) 15 branches/1000 C's, M_(n)=23,300; GPCM_(n)=15,900, M_(w)=74,200.

Example 6

Ethylene Polymerization with VII: The dibromide complex VII (10 mg,0.016 mmol) was suspended in toluene (50 ml). The suspension wasequilibrated at 0° C. in an ice water bath under 1 atm of ethylene, thentreated with MAO (2 ml, 10 wt % solution in toluene) and stirredvigorously under 1 atm of ethylene at 0° C. After 1 hr., the reactionwas quenched by sequential addition of acetone, methanol and 6 N HCl.The resulting polymer was filtered and dried in vacuo to afford 944 mgof polyethylene (2100 TO/hr). ¹H NMR (400 MHz, o-dichlorobenzene-d₄) 46branches/1000 C's, M_(n)=12,860; GPC M_(n)=12,800, M_(w)=39,700.

Example 7

Ethylene Polymerization with VII: The dibromide complex VII (10.5 mg)was suspended in toluene (50 ml). The suspension was equilibrated atroom temperature (immersed in a water bath) under 1 atm of ethylene for10 min, then treated with MAO (2 ml, 10 wt % solution in toluene). Theresulting solution was stirred vigorously under 1 atm of ethylene atroom temperature for 30 min, then quenched by the sequential addition ofacetone, methanol, and 6N HCl. The resulting polymer was filtered anddried in vacuo to afford 878 mg of polyethylene (3300 TO/hr). ¹H NMR(400 MHz, o-dichlorobenzene-d₄) 70 branches/1000 C's, M_(n)=6300; GPCM_(n)=7360, M_(w)=14,400.

Example 8

Ethylene Polymerization with VII: The dibromide complex VII (3 mg,0.0054 mmol) was charged to a stainless steel Parr® autoclave, which wasthen evacuated and backfilled with ethylene. Toluene (300 ml) and MAO (2ml, 10 wt % solution in toluene) were added sequentially with vigorousstirring. The reactor was rapidly pressurized to 600 psig ethylene andheated to ˜45° C. Over ˜5 min, the pressure reached 800 psig ethylene.After 13 min of vigorous stirring, the rupture valve on the reactorblew, resulting in a loss of ˜⅓ of the volume of the reactor. Theremaining suspension was filtered and dried in vacuo to afford 1.07 g ofpolyethylene (48,850 TO/hr based on a loss of 33% of the volume of thereactor). ¹H NMR (400 MHz, o-dichlorobenzene-d₄) 36 branches/1000 C's,M_(n) =9,670; GPC M _(n)=9,730, M_(w)=25,500.

Example 9

Synthesis of VIII: A solution of 2-dipyridyl ketone (1 g, 5.43 mmol) inTHF (16 ml) was added via cannula with stirring to a solution of phenylmagnesium bromide (5.97 ml, 1 M in THF) in THF (16 ml). The resultingsuspension was stirred at room temperature for 18 hr, then quenched withaqueous saturated NH₄Cl (25 ml). The volatiles were removed in vacuo andthe residue was partitioned between CH₂Cl₂ (25 ml) and H₂O (25 ml). Theaqueous layer was further extracted with CH₂Cl₂ (2×25 ml). The combinedorganic layers were washed with brine (25 ml) dried over Na₂SO₄ filteredand concentrated in vacuo to afford an oil, which crystallized onstanding. The resulting crystals were filtered, washed with methanol anddried in vacuo to afford VIII (572 mg, 40%) as white crystals: FDMS m/z262 (M+).

Example 10

Synthesis of IX: Alcohol VIII (108.5 mg, 0.414 mmol) was charged to a 50ml Schlenck tube and pumped into an Ar filled glove box. The tube wascharged with (DME)NiBr₂ (101 mg, 0.331 mmol), capped with a septum andremoved from the box. CH₂Cl₂ (10 ml) was added to the tube and theresulting solution was stirred under Ar overnight. The CH₂Cl₂ wasremoved under a stream of Ar, the resulting solid was washed withhexanes (2×10 ml) and dried in vacuo to afford IX as a green solid.

Example 11

Ethylene Polymerization with IX: A suspension of dibromide complex IX(9.5 mg, 0.0196 mmol) in toluene (50 ml) was allowed to equilibrate at0° C. under 1 atm of ethylene, then treated with MAO (2 ml, 10 wt %solution in toluene). The resulting suspension was stirred vigorously at0° C. under 1 atm of ethylene for 11 min, then quenched by thesequential addition of acetone, methanol, and 6 N HCl. The resultingpolymer was filtered and dried in vacuo to afford 63 mg of polyethylene(690 TO/hr). GPC M_(n)=910, M_(w)=2230.

Example 12

Synthesis of X: A 1 ml portion of a solution of 4-bromobiphenyl (900.6mg, 3.86 mmol) in Et₂O (5 ml) and tetrahydrofuran (THF) (1 ml) was addedto a suspension of Mg turnings (93.9 mg, 3.86 mmol) in Et₂O (5 ml).1,2-Dibromethane (0.25 ml) was added. After initiation, the remainder ofthe 4-bromobiphenyl solution was added in 1 ml portions. The reactionwas then stirred at room temperature for 1 hr, heated to reflux for 2 hrand cooled to rt. A solution of 2-dipyridyl ketone (741 mg, 4.02 mmol)in Et₂O (5 ml) was added, resulting in the immediate formation of aprecipitate. Additional THF (5 ml) was added, and the suspension stirredat rt. After 2 hr, the reaction was quenched with saturated aqueousNH₄Cl, and extracted with CH₂Cl₂. The combined organic layers were driedover MgSO₄, filtered and concentrated in vacuo to afford X as an oil,which crystallized on standing: FDMS m/z 339 (M+1).

Example 13

Synthesis of XI: A mixture of (DME)NiBr₂ (76 mg, 0.246 mmol) and alcoholX (100 mg, 0.295 mmol) was dissolved in CH₂Cl₂ (2 ml). The resultingsolution was stirred at rt under Ar for 45 min. The CH₂Cl₂ was removedin vacuo to afford XI as a solid.

Example 14

Ethylene Polymerization with XI: A suspension of dibromide complex XI(11 mg, 0.0197 mmol) in toluene (50 ml) was allowed to equilibrate at 0°C. under 1 atm of ethylene, then treated with MAO (2 ml, 10 wt %solution in toluene). The resulting solution was stirred vigorously at0° C. under 1 atm of ethylene for 30 min, then quenched by thesequential addition of acetone, ethanol, and 6 N HCl. The resultingpolymer was filtered and dried in vacuo to afford 206.5 mg ofpolyethylene (800 TO/hr). GPC M_(n)=4440, M_(w)=11,200.

Example 15

Synthesis of XII: To a stirred room temperature suspension of Mgturnings (97.8 mg, 4.02 mmol) in tetrahydrofuran (5 ml) was added1,2-dibromoethane (0.15 ml) and a 1 ml portion of a solution of2-bromonaphthalene (803.2 mg, 3.88 mmol) in tetrahydrofuran (5 ml). Thesuspension was warmed slightly to initiate the reaction then the rest ofthe 2-bromonaph tale ne solution was added in 1 ml portions over 20 min.The reaction was heated at reflux for an additional 20 mm, then cooledto room temperature and treated with a solution of 2-dipyridyl ketone(715 mg, 3.88 mmol) in tetrahydrofuran (5 ml). The resulting suspensionwas stirred at room temperature for 50 min an d at reflux for 15 min,after which it was cooled to room temperature and quenched with aq.saturated NH₄Cl and extracted with Et₂O. The combined organic layerswere dried over MgSO₄, filtered and dried in vacuo. The residue waschromatographed (SiO₂, 3/1 hexane/ethyl acetate) to afford XII (195.6mg, 16%): R_(f) 0.24 (3/1 hexane/ethyl acetate); FDMS m/z 312 (M+).

Example 16

Synthesis of XIII: A solution of XII (97.8 mg, 0.31 mmol) in CH₂Cl₂ (10ml) was added to dry (DME)NiBr₂ (90.0 mg, 0.294 mmol) under nitrogen atroom temperature. The resulting solution was stirred at room temperaturefor 45 min., t hen concentrated in vacuo to afford XIII as a greenpowder.

Example 17

Ethylene Polymerization with XII: A suspension of dibromide complex XIII(11 mg, 0.020 mmol) in toluene (50 ml) was allowed to equilibrate at 0°C. under 1 atm of ethylene, then treated with MAO (2 ml, 10 wt %solution in toluene). The resulting solution was stirred vigorously at0° C. under 1 atm of ethylene for 30 min, then quenched by thesequential addition of acetone, methanol, and 6 N HCl. The resultingpolymer was filtered and dried in vacuo to afford 160.8 mg ofpolyethylene (575 TO/hr). GPC M_(n)=4180, M_(w)=16,600.

Example 18

Synthesis of XIV: To a stirred suspension of Mg turnings (488 mg, 20mmol) in Et₂O (2.6 ml) was added a 0.20 ml portion of a solution of2-bromothiazole (0.458 ml, 5.1 mmol) in 1,2-dibromoethane (1.32 ml, 15mmol). The resulting suspension was stirred at room temperature for 30min. The remainder of the 2-bromothiazole solution was added in 0.10 mlportions at a rate such that a gentle reflux was maintained. After thefinal addition, the reaction was stirred at room temperature for 30 min,then treated with a solution of 2-phenyl ethyl benzoate (0.524 ml, 2.55mmol) in Et₂O (4 ml). The resulting suspension was stirred at roomtemperature for 3.5 hr, then quenched with aqueous saturated NH₄Cl (25ml) and extracted with CH₂Cl₂ (2×25 ml). The combined organic layerswere dried over Na₂SO₄, filtered and concentrated in vacuo. The residuewas flash chromatographed (SiO₂, 12% ethyl acetate/hexanes followed by25% ethyl acetate/hexanes) to afford XIV (143 mg, 1.6%): R_(f) 0.07 (12%ethyl acetate/hexanes).

Example 19

Synthesis of XV: To (DME)NiBr₂ (100 mg, 0.33 mmol) was added a solutionof XIV (143 mg, 0.41 mmol) in CH₂Cl₂ (19 ml). The resulting solution wasstirred at room temperature for 1.5 hr. The solvent was removed under astream of Ar and the residue was dried in vacuo to afford XV as abrown/green solid.

Example 20

Ethylene polymerization with XV: A suspension of dibromide complex XV(10.8 mg, 0.019 mmol) in toluene (50 ml) was allowed to equilibrate at0° C. under 1 atm of ethylene, then treated with MAO (2 ml, 10 wt %solution in toluene). The resulting solution was stirred vigorously at0° C. under 1 atm of ethylene for 200 min, then quenched by thesequential addition of acetone, methanol, and 6 N HCl. The resultingpolymer was filtered and dried in vacuo to afford 243.9 mg ofpolyethylene (138 TO/hr). GPC M_(n)=860, M_(w)=3080.

Example 21

Synthesis of XVI: A solution of 2-pyridylacetonitrile (0.472 ml, 4.23mmol) in DMF (41 ml) was treated with NaH (677 mg, 17 mmol, 60%dispersion in mineral oil) and stirred under Ar for 30 min. Theresulting suspension was treated with chloropyrazine (0.378 ml, 4.23mmol) and heated to 90° C. for 5 hr. The reaction was then cooled toroom temperature, quenched with H₂O (100 ml) and extracted with CH₂Cl₂(2×100 ml). The combined organic layers were dried over Na₂SO₄, filteredand concentrated in vacuo. The residue was flash chromatographed (SiO₂,4% methanol/CH₂Cl₂) to afford XVI (713.9 mg, 86%): R_(f) 0.5 (4%methanol/CH₂Cl₂); FDMS m/z 196 (M+).

Example 22

Synthesis of XVII: An ice cold solution of XVI (215 mg, 1.1 mmol) inCHCl₃ (48 ml) was treated with 3-chloroperoxybenzoic acid (387 mg, 1.6mmol). The resulting solution was stirred overnight, allowing the icebath to expire, then quenched with 0.5 M NaOH (50 ml). The organic layerwas removed and washed with brine (50 ml). The combined aqueous layerswere further extracted with CH₂Cl₂ (2×40 ml). The combined organiclayers were dried over Na₂SO₄, filtered and concentrated in vacuo toafford XVII (169.1 mg, 83%) as a yellow solid: FDMS m/z 185 (M+).

Example 23

Synthesis of XVII: A suspension of Mg turnings (12 mg, 0.49 mmol) inEt₂O (0.5 ml) was treated with a 0.25 ml of a solution of2-bromobiphenyl (0.0591 ml, 0.343 mmol) in Et₂O (0.5 ml) and1,2-dibromoethane (0.006 ml). After initiation, the remaining2-bromobiphenyl solution was added, and the suspension heated at refluxfor 1 hr. The resulting suspension was cooled to room temperature, andtreated with a solution of XVII (63.4 mg, 0.343 mmol) in Et₂O (0.5 ml)and THF (1.0 ml). The suspension was stirred under Ar at roomtemperature for 1 hr, then quenched with aqueous saturated NH₄Cl (10 ml)and extracted with CH₂Cl₂ (2×10 ml). The combined organic layers weredried over Na₂SO₄, filtered and concentrated in vacuo. The residue wasflash chromatographed (SiO₂, 20% ethyl acetate/hexanes followed by 40%ethyl acetate/hexanes) to afford XVIII (25 mg, 22%): R_(f) 0.58 (50%ethyl acetateihexanes); FDMS m/z 339 (M+).

Example 24

Synthesis of XIX: To (DME)NiBr₂ (18 mg, 0.0588 mmol) was added asolution of XVIII (25 mg, 0.074 mmol) in CH₂Cl₂ (5 ml). The resultingsolution was stirred at room temperature under Ar for 30 min, thenconcentrated in vacuo to afford XIX as a green solid.

Example 25

Ethylene Polymerization with XIX: A solution of dibromide complex XIX(9.0 mg, 0.016 mmol) in toluene (100 ml) was allowed to equilibrate at0° C. under 1 atm of ethylene, then treated with MAO (4 ml, 10 wt %solution in toluene). The resulting solution was stirred vigorously at0° C. under 1 atm of ethylene for 30 min, then quenched by thesequential addition of acetone, methanol, and 6 N HCl. The resultingpolymer was filtered and dried in vacuo to afford 1.13 g of polyethylene(5,027 TO/hr). ¹H NMR (400 MHz, o-dichlorobenzene-d₄) 7 branches/1000C's, M_(n)=13,700; GPC M_(n)=15,700, M_(w)=127,900.

Example 26

Ethylene Polymerization with XIX: A solution of dibromide complex XIX(7.0 mg, 0.0125 mmol) in toluene (100 ml) was allowed to equilibrate at23° C. under 1 atm of ethylene, then treated with MAO (4 ml, 10 wt %solution in toluene). The resulting solution was stirred vigorously at23° C. under 1 atm of ethylene for 15 min, then quenched by thesequential addition of acetone, methanol, and 6 N HCl. The resultingpolymer was filtered and dried in vacuo to afford 600.3 mg ofpolyethylene (6860 TO/hr): ¹H NMR (400 MHz, o-dichlorobenzene-d₄) 28branches/1000 C's; GPC M_(n)=5750, M_(w)=66,300.

We claim:
 1. A compound of formula II:

wherein L¹ and L² are each, independently, a 5- or 6-membered,monodentate N-donor, heterocyclic ring connected to Q at the positionadjacent to the donor nitrogen; Q is a group of the formula —C(Y)(Z)—wherein Z is H or a heteroatom connected monoradical and Y ishydrocarbyl or substituted hydrocarbyl; T is H or hydrocarbyl; L is amono-olefin or a neutral Lewis base wherein the coordinated atom isnitrogen, oxygen, or sulfur; M is Ni(II), Pd(II), Co(II), or Fe(II); andX⁻ is a weakly coordinating anion.
 2. The compound of claim 1 wherein Mis Ni(II).
 3. The compound of claim 2 wherein Z is —OH, —SH, —OR³,—OAlR⁴ ₂, —OSiR⁴ ₃, —O(silica surface), —O(methylaluminoxane),—OB(OR⁴)₂, —SR⁴, or —NR⁴ ₂, where R³ is hydrocarbyl or substitutedhydrocarbyl and R⁴ is hydrocarbyl or substituted hydrocarbyl.
 4. Thecompound of claim 3 wherein L¹ and L² are each independently, selectedfrom the group consisting of

wherein: E is selected from H, —OCH₃, —NO₂, —CN, —SO₂R⁶, —CO₂R⁶, and—CONR⁶ ₂ where R⁶ is hydrocarbyl or substituted hydrocarbyl; and, R⁵ ishydrocarbyl or substituted hydrocarbyl.
 5. The compound of claim 4,wherein L¹ and L² are each, independently, selected from the groupconsisting of

wherein R⁵ is hydrocarbyl or substituted hydrocarbyl.
 6. The compound ofclaim 5, wherein Y is selected from the group consisting of

wherein R⁷ is hydrocarbyl or substituted hydrocarbyl.
 7. The compound ofclaim 6 having the formula IV

wherein: T is hydrogen or hydrocarbyl; L is a mono-olefin or a neutralLewis base wherein the coordinated atom is nitrogen, oxygen, or sulfur;M is Ni(II); and X⁻ is a weakly coordinating anion.
 8. The compound ofclaim 6 having the formula IV

wherein: T is hydrogen or hydrocarbyl; L is a mono-olefin or a neutralLewis base wherein the coordinated atom is nitrogen, oxygen, or sulfur;M is Ni(II); and X⁻ is a weakly coordinating anion.
 9. A compound offormula III:

wherein L¹ and L² are each, independently, a 5- or 6-membered,monodentate N-donor, heterocyclic ring connected to Q at the positionadjacent to the donor nitrogen; Q is a group of the formula —C(Y)(Z)—wherein Z is H or a heteroatom connected monoradical and Y ishydrocarbyl or substituted hydrocarbyl; U is alkyl, chloride, iodide, orbromide; W is alkyl, chloride, iodide, or bromide; and M is Ni(II),Pd(II), Co(II), or Fe(II).
 10. The compound of claim 9 wherein M isNi(II).
 11. The compound of claim 10 wherein Z is —OH, —SH, —OR³, —OAlR⁴₂, —OSiR⁴ ₃, —O(silica surface), —O(methylaluminoxane), —OB(OR⁴)₂, —SR⁴,or —NR⁴ ₂, where R³ is hydrocarbyl or substituted hydrocarbyl and, R⁴ ishydrocarbyl or substituted hydrocarbyl.
 12. The compound of claim 11wherein L¹ and L² are each independently, selected from the groupconsisting of

wherein: E is selected from H, —OCH₃, —NO₂, —CN, —SO₂R⁶, —CO₂R⁶, and—CONR⁶ ₂ where R⁶ is hydrocarbyl or substituted hydrocarbyl; and, R⁵ ishydrocarbyl or substituted hydrocarbyl.
 13. The compound of claim 12,wherein L¹ and L² are each, independently, selected from

wherein R⁵ is hydrocarbyl or substituted hydrocarbyl.
 14. The compoundof claim 10, wherein Y is selected from

wherein R⁷ is hydrocarbyl or substituted hydrocarbyl.
 15. The compoundof claim 14 having the formula V

wherein: U is alkyl, chloride, iodide, or bromide; W is alkyl, chloride,iodide, or bromide; and M is Ni(II).
 16. The compound of claim 14 havingthe formula V

wherein: U is alkyl, chloride, iodide, or bromide; W is alkyl, chloride,iodide, or bromide; and M is Ni(II).
 17. A composition comprising (a) aGroup 8-10 transition metal M, (b) one or more Lewis acids, and (c) abinucleating or multinucleating compound of the formula I:

wherein the Lewis acid or acids are bound to one or more heteroatomswhich are π-conjugated to the donor atom or atoms bound to thetransition metal M; L¹ and L² are each, independently, a 5- or6-membered, monodentate N-donor, heterocyclic ring connected to Q at theposition adjacent to the donor nitrogen; Q is a group of the formula—C(Y)(Z)— wherein Z is H or a heteroatom connected monoradical and Y ishydrocarbyl or substituted hydrocarbyl.
 18. The composition of claim 17wherein L¹ is selected from

and L² is selected from

wherein: E is selected from —OCH₃, —NO₂, —CN, —SO₂R⁶, —CO₂R⁶ ₂ where R⁶is hydrocarbyl or substituted hydrocarbyl; and, R⁵ is hydrocarbyl orsubstituted hydrocarbyl.
 19. The composition of claim 18, wherein L¹ isselected from

and L² is selected from

wherein R⁵ hydrocarbyl or substituted hydrocarbyl.
 20. The compositionof claim 19, wherein Y is selected from

wherein R⁷ is hydrocarbyl or substituted hydrocarbyl.
 21. Thecomposition of claim 20, wherein the compound of formula I is


22. A supported catalyst comprising the reaction product of a compoundof formula III

wherein L¹ and L² are each, independently, a 5- or 6-membered,monodentate N-donor, heterocyclic ring connected to Q at the positionadjacent to the donor nitrogen; Q is a group of the formula —C(Y)(Z)—wherein Z is H or a heteroatom connected monoradical and Y ishydrocarbyl or substituted hydrocarbyl; U is alkyl, chloride, iodide orbromide; W is alkyl, chloride, iodide or bromide; M is Ni(II), Pd(II),Co(II), or Fe(II); and, with a solid support which has been pre-treatedwith a compound A, wherein A is selected from the group consisting of aneutral Lewis acid capable of abstracting U⁻ or W⁻ to form a weaklycoordinating anion, a cationic Lewis acid whose counterion is a weaklycoordinating anion, and a Bronsted acid whose conjugate base is a weaklycoordinating anion.
 23. The catalyst of claim 22, wherein L¹ and L² areeach, independently, selected from

wherein R⁵ is hydrocarbyl or substituted hydrocarbyl.
 24. The catalystof claim 23 wherein Y is selected from

wherein R⁷ is hydrocarbyl or substituted hydrocarbyl.
 25. The catalystof claim 24, wherein the compound of formula III is:

wherein U is alkyl, chloride, iodide or bromide; W is alkyl, chloride,iodide or bromide; and, M is Ni(II).
 26. The catalyst of claim 24,wherein the compound of formula III is:

wherein U is alkyl, chloride, iodide or bromide; W is alkyl, chloride,iodide or bromide; and, M is Ni(II).
 27. The supported catalyst of claim25 wherein the support is silica and the compound A ismethylaluminoxane.
 28. The supported catalyst of claim 26 wherein thesupport is